TWI660846B - Laminated body manufacturing method - Google Patents

Abstract

The present invention provides a laminated body capable of forming a polarizing film with uniformized properties. The laminated body manufacturing method of the present invention includes a step of heating a resin substrate to a glass transition temperature (Tg) of the resin substrate of -15 ° C or higher, and a step of forming a polyvinyl alcohol-based resin layer on the resin substrate. .

Description

Laminated body manufacturing method Field of invention

The present invention relates to a method for manufacturing a laminated body. Specifically, this invention relates to the manufacturing method of the laminated body which has a resin base material and the polyvinyl alcohol (PVA) -type resin layer formed on this resin base material.

Background of the invention

A method has been proposed in which a polarizing film is produced by applying a PVA-based resin layer on a resin substrate and stretching and dyeing the laminated body (such as Patent Document 1, Patent Document 2). A thinner polarizing film can be produced according to the method described above, and therefore attracts attention because it contributes to a reduction in thickness of an image display device, for example. However, in this case, there is a problem that the properties (specifically, film thickness, optical characteristics, and appearance) of the obtained polarizing film are inconsistent.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 51-69644

Patent Document 2: Japanese Patent Laid-Open No. 2001-343521

Summary of invention

This invention is made in order to solve the said conventional problem, The main objective is to provide the laminated body which can manufacture the polarizing film with a uniform performance.

The method for producing a laminated body of the present invention includes a step of heating a resin substrate to a glass transition temperature (Tg) of the resin substrate of -15 ° C or higher, and forming a polyvinyl alcohol-based resin on the resin substrate. Layer of steps.

In one embodiment, the resin substrate is rolled out from a resin substrate roll formed by winding a long resin substrate into a roll shape, and the heating step is performed.

In one embodiment, the heating step is performed after storage in the coiled state.

In one embodiment, the unwinding step, the heating step, and the polyvinyl alcohol-based resin layer forming step are continuously performed.

In one embodiment, the heating step is performed at a glass transition temperature (Tg) of the resin substrate + 15 ° C or lower.

In one embodiment, the resin substrate is conveyed by a conveyance roller provided in a heating furnace, and the heating step is performed at the same time.

In one embodiment, the holding angle of the conveyance roller in the heating furnace is 90 ° or more.

In one embodiment, the distance between the centers of the transport rollers in the heating furnace is 2 m or less.

In one embodiment, the resin substrate is conveyed by a tenter, and the heating step is performed at the same time.

In one embodiment, the shrinkage ratio of the resin substrate by the heating is 3% or less.

In one embodiment, the resin substrate is made of a polyethylene terephthalate resin.

In one embodiment, the resin substrate is stretched in advance.

In one embodiment, the polyvinyl alcohol-based resin layer is formed by applying a coating solution containing a polyvinyl alcohol-based resin on the resin substrate by a die coating method and drying the coating liquid.

According to another aspect of the present invention, a method for manufacturing a polarizing film can be provided. The manufacturing method of this polarizing film uses the laminated body obtained by the said manufacturing method.

In one embodiment, a step of stretching the laminated body is included.

According to still another aspect of the present invention, a method for manufacturing a polarizing plate can be provided. The manufacturing method of the polarizing plate includes a step of laminating a protective film on a polarizing film, and the polarizing film is manufactured according to the above manufacturing method.

According to still another aspect of the present invention, a stretched laminate can be provided. The stretched laminate has a resin substrate and a polyvinyl alcohol-based resin layer formed on the resin substrate. The film thickness of the polyvinyl alcohol-based resin layer is not more than 0.25 μm in a size of 200 mm (MD) × 200 mm (TD), and the polyvinyl alcohol-based resin layer is in a size of 200 mm (MD) × 200 mm (TD) The hysteresis axis is inconsistent below 0.50 °.

According to still another aspect of the present invention, a manufacturing apparatus for a laminated body can be provided.

In one embodiment, the manufacturing apparatus includes a winding mechanism, a heating furnace, and a coating mechanism. The winding mechanism is configured to roll out a resin substrate roll formed by winding a long resin substrate into a roll shape. Resin substrate; the heating furnace is provided with a conveying roller for conveying the long resin substrate, and the heating The furnace system heats the resin substrate to a glass transition temperature (Tg) of the resin substrate of -15 ° C or higher; the coating mechanism applies a coating solution containing a polyvinyl alcohol resin to the heated resin substrate.

In one embodiment, the resin substrate is conveyed by a conveyance roller provided in the heating furnace, and is simultaneously heated.

In one embodiment, the holding angle of the conveyance roller in the heating furnace is 90 ° or more.

In one embodiment, the distance between the centers of the transport rollers in the heating furnace is 2 m or less.

In one embodiment, the manufacturing apparatus includes a unwinding mechanism, a heating mechanism, and a coating mechanism; the unwinding mechanism rolls out a resin substrate roll formed by winding a long resin substrate into a roll shape. Resin substrate; the heating mechanism is provided with a tenter for holding both ends of the elongated resin substrate for conveying, and the heating mechanism is for holding both ends of the tenter by the clamps of the tenter The resin substrate is heated to a glass transition temperature (Tg) of the resin substrate of -15 ° C or higher; the coating mechanism is configured to apply a coating solution containing a polyvinyl alcohol resin to the heated resin substrate.

In one embodiment, the resin substrate is conveyed by the tenter and heated at the same time.

According to the present invention, by subjecting the resin substrate to a heat treatment at a predetermined temperature or higher, it is possible to reduce (unify) the surface unevenness of the resin substrate (for example, a gauge band generated when the resin substrate is rolled up). As a result, a PVA-based resin layer with good thickness uniformity can be formed on the resin substrate. Correct By performing various treatments on the PVA-based resin layer with good thickness uniformity in this way, a polarizing film with excellent uniformity (specifically, film thickness, optical characteristics, and appearance) and excellent uniformity (for example, which fully meets the requirements of liquid crystal televisions) can be manufactured. Quality).

10‧‧‧ laminated body

11‧‧‧ resin substrate

12‧‧‧Polyvinyl alcohol (PVA) resin layer

100‧‧‧Laminated body manufacturing device

21‧‧‧Clamp

30‧‧‧Resin base roll

40‧‧‧ unwinding roller

50‧‧‧Heating device

60‧‧‧coating device

70‧‧‧ drying device

80‧‧‧ Roller Roller

90‧‧‧ transport roller

A‧‧‧ Oven

R1, R2, R3, R4, R5, R6 ‧‧‧ free roller

W ₀ , W ₁ ‧‧‧Width

θ ‧‧‧ holding angle

FIG. 1 is a schematic cross-sectional view of a laminated body according to an embodiment of the present invention.

2 (a) and 2 (b) are schematic diagrams illustrating a method for heating a resin substrate in an embodiment.

FIG. 3 is a schematic diagram illustrating a method for heating a resin substrate in another embodiment.

Fig. 4 is a schematic diagram showing an example of the present invention.

5 (a) and 5 (b) are schematic diagrams illustrating a method for evaluating the appearance of a PVA-based resin layer.

Forms used to implement the invention

Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

A. Laminate

FIG. 1 is a schematic cross-sectional view of a laminated body according to an embodiment of the present invention. The laminated body 10 is produced by forming a polyvinyl alcohol (PVA) -based resin layer 12 on a resin substrate 11.

A-1. Resin substrate

The resin substrate is typically elongated. Better resin substrate thickness It is 20 μm to 300 μm, and more preferably 50 μm to 200 μm.

Examples of the material for forming the resin substrate include polyethylene terephthalate. Ester-based resins such as diester-based resins, cycloolefin-based resins, olefin-based resins such as polypropylene, (meth) acrylic resins, polyamide resins, polycarbonate resins, and copolymer resins thereof and the like. Preferably, a polyethylene terephthalate-based resin is used. Among them, an amorphous polyethylene terephthalate resin is preferably used. Specific examples of the amorphous polyethylene terephthalate resin include a copolymer further containing isophthalic acid as a dicarboxylic acid or a copolymer further containing cyclohexanedimethanol as a glycol.

The glass transition temperature (Tg) of the resin substrate is preferably 170 ° C or lower. By using the resin substrate described above, it is possible to stretch the laminated body at a temperature at which the crystallization of the PVA-based resin does not accelerate rapidly, and to suppress problems caused by the crystallization (for example, hindering PVA caused by stretching). Orientation of the resin layer). In addition, the glass transition temperature of the resin substrate is preferably 60 ° C or higher. The glass transition temperature (Tg) is a value determined based on JIS K 7121.

The resin substrate may be formed by any appropriate method. Forming party Examples of the method include a melt extrusion method, a solution casting method (solution casting method), a calendering method, and a compression molding method. Among them, melt extrusion is preferred.

Surface modification treatments (such as corona Treatment, etc.), and an easy-adhesion layer may be formed. With the above treatment, the adhesion between the resin substrate and the PVA-based resin layer can be improved. The surface modification treatment and / or the formation of an easy-adhesion layer may be performed before the heat treatment described later, or may be performed after the heat treatment. In addition, if the stretching described later is performed, it may be performed before the stretching, or may be performed after the stretching.

In one embodiment, the tree is stretched before the heat treatment described later. Grease substrate. The resin substrate may be stretched by any appropriate method. Specifically, fixed-end stretching or free-end stretching can be used. Also, simultaneous biaxial stretching or sequential biaxial stretching may be used. The stretching of the resin substrate can be performed in one stage or in multiple stages. When carried out in multiple stages, the stretching ratio of the resin substrate described later is the product of the stretching ratios at each stage. In addition, the stretching method is not particularly limited, and may be an aerial stretching method or an underwater stretching method.

The stretching direction of the resin substrate can be appropriately set. E.g. The strip-shaped resin substrate is stretched in the width direction. Specifically, the resin substrate is transported in the longitudinal direction and stretched in a direction (TD) orthogonal to the transport direction (MD). In this specification, the term "orthogonal" also includes a substantially orthogonal form. Here, the term “substantially orthogonal” includes a case of 90 ° ± 5.0 °, preferably 90 ° ± 3.0 °, and more preferably 90 ° ± 1.0 °. By stretching the resin substrate in the width direction (TD), the resin substrate can be effectively used. In addition, the thickness of the resin substrate in the TD can be made uniform, and the inconsistency in part of the film thickness described later can be suppressed.

The stretching temperature of the resin substrate can be adapted to the forming material of the resin substrate Material, stretching method, etc. to any appropriate value. The typical stretching temperature is preferably Tg-10 ° C to Tg + 80 ° C relative to the glass transition temperature (Tg) of the resin substrate. When a polyethylene terephthalate resin is used as a material for forming the resin substrate, the stretching temperature is preferably 70 ° C to 150 ° C, and more preferably 90 ° C to 130 ° C.

The stretching ratio of the resin substrate should be relative to the original length of the resin substrate Degree is 1.5 times or more. By setting the above range, it is possible to suppress The case where the film thickness is inconsistent is described. The stretching ratio of the resin substrate is preferably 3.0 times or less with respect to the original length of the resin substrate. By setting it as the said range, generation | occurrence | production of a wrinkle in the heating process mentioned later can be suppressed well.

A-2. Curling and storage

In one embodiment, the long resin substrate is rolled into a roll shape. When the resin base material is molded, a part of the film thickness may be inconsistent. Rolling in this state may cause unevenness in the resin base material. Typical coil tension is 60N / m to 150N / m (unit: N / m is the tension per unit width and length). The rolled resin base material can be kept (stored) in a rolled state for any appropriate period before being supplied to the next step. For example, when the PVA-based resin layer is not (unable to) be continuously formed after the resin substrate is formed, the resin substrate is kept in a rolled state and stored. Once the storage period becomes longer (for example, more than 3 days), the occurrence of unevenness (the degree of unevenness and the number of unevenness) becomes significant, and the PVA-based resin layer (laminated body) produced has inconsistent film thickness. tendency. Therefore, the longer the storage period of the resin substrate roll, the more significant the effect of the heat treatment described below can be obtained. In addition, the resin substrate roll can be stored in any appropriate gas environment. The storage temperature is, for example, 15 ° C to 35 ° C. The relative humidity is, for example, 40% RH to 80% RH.

A-3. Heating

The resin substrate is heated. Specifically, the resin substrate is heated with hot air, an infrared heater, a roller heater, or the like. The heating temperature is the glass transition temperature (Tg) of the resin substrate of -15 ° C or higher, preferably Tg-10 ° C or higher, and more preferably Tg-5 ° C or higher. When using a polyethylene terephthalate resin as the material for forming the resin substrate, the heating temperature is preferably 68 ° C or higher. By By heating the resin substrate at the above temperature, the unevenness on the surface of the resin substrate can be alleviated (homogenized). As a result, a PVA-based resin layer described later can be formed satisfactorily, and a PVA-based resin layer having good thickness uniformity can be formed. In addition, the heating temperature is preferably (Tg) + 15 ° C or lower, and more preferably (Tg) + 10 ° C or lower. When using a polyethylene terephthalate resin as the material for forming the resin substrate, the heating temperature is preferably 80 ° C or lower. By heating the resin substrate at the above-mentioned temperature, the occurrence of wrinkles (thermal wrinkles) can be satisfactorily suppressed.

The heating time is preferably 70 seconds to 150 seconds, and more preferably 75 seconds to 100 seconds.

The resin substrate can shrink due to heating. For example, when the resin substrate is stretched in the width direction before heating, the resin substrate may shrink in the width direction (TD shrinkage) due to heating. The shrinkage (TD shrinkage) of the resin substrate should preferably be 3% or less, more preferably 2% or less, and even more preferably 1.5% or less. When the shrinkage rate is in the above range, the occurrence of wrinkles is suppressed and a good appearance can be obtained. The TD shrinkage is calculated by the following formula.

TD shrinkage (%) = {1-(width of resin substrate after heating (W ₁ ) / width of resin substrate before heating (W ₀ ))) × 100

In one embodiment, the resin substrate is heated while being conveyed. When the resin base material has been rolled into a roll shape as described above, it is preferable to apply heat treatment to the resin base material rolled out from the resin base material roll. Examples of the heating method include a method of conveying a resin substrate by a conveyance roller provided in a heating furnace, and a method of heating the resin substrate while conveying the resin substrate by a tenter. With the former, the size of the equipment can be suppressed. With the latter, the occurrence of wrinkles can be suppressed extremely well.

Figures 2 (a) and 2 (b) show the details when using the transfer roller. example. In the example shown in the figure, the resin substrate 11 is conveyed in the longitudinal direction by the free rollers R2 to R5 provided in the oven A, thereby heating the resin substrate 11. From the viewpoint of production speed, it is preferable to install four or more free rollers in the oven as shown in the example.

The holding angle of the free roller in the oven should be above 90 ° C. Hutu In the example shown in 2 (a), the holding angle θ of the free rollers R2 and R5 is set to 90 °, and the holding angle θ of the free rollers R3 and R4 is set to 180 °. In the example shown in FIG. 2 (b), the holding angle θ of the free rollers R2 to R5 is set to 90 °. By setting the holding angle as described above, the shrinkage of the resin substrate is suppressed, and the occurrence of wrinkles can be suppressed. The angle of hold is a straight line connecting the center point of the free roller and the starting point of contact between the resin base material and the free roller when the free roller is viewed from a section perpendicular to the axial direction, The angle formed by the straight line of the contact end point of the resin substrate and the free roller. The interval between the free rollers in the oven (the distance between the centers of the rollers) should be 2m or less. In addition, the distance between the two free rollers (between R1-R2 and R5-R6 in the example shown in the figure) should be less than 2m. By setting the interval as described above, shrinkage of the resin substrate is suppressed, and occurrence of wrinkles can be suppressed. In this embodiment, the shrinkage of the resin substrate is also related to the stretching ratio of the resin substrate, the heating temperature, and the like.

A specific example when a tenter is used is shown in FIG. 3. Example In the middle, the clamps 21 and 21 on the left and right sides of the tenter respectively hold the two ends of the resin base material 11 (located on a line orthogonal to the conveying direction), and carry the resin at a predetermined speed in the length direction to heat the resin Substrate 11. Transport direction The distance between the clamps (the distance between the ends of adjacent clamps) should be less than 20mm, and more preferably less than 10mm. The width of the clamp should be more than 20mm, and more preferably 30mm. In this embodiment, the TD shrinkage of the resin substrate can be controlled by, for example, adjusting the distance between the left and right clamps. Specifically, when the distance between the left and right clamps is moved without changing, the TD shrinkage rate is substantially 0%. Conversely, by widening the distance between the left and right clamps, the resin substrate can be stretched by TD. The TD change rate of the resin substrate should be more than 1.00 times, and more preferably 1.00 times to 1.10 times. The TD change rate is calculated by the following formula.

TD change rate (times) = resin substrate width (W ₁ ) after heating / resin substrate width (W ₀ ) before heating

A-4. Formation of PVA-based resin layer

As the PVA-based resin forming the PVA-based resin layer, any appropriate resin can be used. Examples include polyvinyl alcohol and ethylene-vinyl alcohol copolymer. Polyvinyl alcohol can be obtained by saponification of polyvinyl ethyl ester. Ethylene-vinyl alcohol copolymers are made by saponification of ethylene-vinyl acetate copolymers. The saponification degree of PVA-based resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, and even more preferably 99.0 mol% to 99.93 mol%. The degree of saponification can be determined based on JIS K 6726-1994. By using the PVA-based resin having the above-mentioned degree of saponification, a polarizing film having good durability can be obtained. When the saponification degree is too high, there is a fear of gelation.

The average degree of polymerization of the PVA-based resin may be appropriately selected depending on the purpose. The average degree of polymerization is usually 1000 to 10,000, preferably 1200 to 4500, and more preferably 1500 to 4300. The average degree of polymerization can be determined based on JIS K 6726-1994.

It is better to apply a coating solution containing PVA resin on the resin substrate Then, it is dried to form a PVA-based resin layer. The coating solution is typically a solution obtained by dissolving the PVA-based resin in a solvent. As the solvent, polyhydric alcohols such as water, dimethylformamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, trimethylolpropane, and ethylene glycol can be used. Amines such as amines and ethylenetriamine. These can be used alone or in combination of two or more kinds. Among them, water is preferred. The PVA-based resin concentration of the solution is preferably 3 to 20 parts by weight based on 100 parts by weight of the solvent. If the resin concentration is used, a uniform coating film adhered to the resin substrate can be formed.

The coating liquid may contain additives. Examples of additives include plasticization Agents, surfactants, etc. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. The surfactant may be a non-ionic surfactant. These can be used for the purpose of further improving the uniformity, dyeability, and stretchability of the PVA-based resin layer to be produced. Moreover, the additive may be exemplified as an easily accessible ingredient. By using the easy-contact component, the adhesion between the resin substrate and the PVA-based resin layer can be improved. As a result, problems such as peeling of the PVA-based resin layer from the resin substrate can be suppressed, and dyeing and stretching in water described later can be performed favorably. Modified PVA such as acetoacetate-based modified PVA can be used as the easy-to-connect component.

The coating liquid may be applied by any appropriate method. For example, a roll coating method, a spin coating method, a bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a doctor blade coating method (comma blade coating method, etc.), and the like can be mentioned.

In one embodiment, a die coating method is used. The die coating method applies a coating liquid by fixing a gap between a resin substrate and a mold (such as a fountain mold or a slit mold), so that a coating film having excellent thickness uniformity can be obtained. another On the one hand, when unevenness occurs in the resin substrate, the distance between the resin substrate and the die lip is not uniform, and it may be difficult to form a uniform coating film. Therefore, when the die coating method is used, the above-mentioned effect of the heat treatment can be remarkably obtained.

Apply the coating solution to a PVA resin that can be dried The layer thickness is preferably 3 μm to 40 μm, and more preferably 3 μm to 20 μm. The coating and drying temperature of the coating liquid is preferably 50 ° C or higher.

The PVA-based resin layer is preferably formed after the above heating. E.g, After heating, the resin substrate is not rolled, and a PVA-based resin layer is formed on the resin substrate. This is because the above heating effect can be obtained satisfactorily.

In addition, before forming a PVA-based resin layer, A primer layer (primer layer) is formed in advance on the PVA-based resin layer forming side. The material constituting the primer layer is not particularly limited as long as it exhibits a certain degree of strong adhesion to both the resin substrate and the PVA-based resin layer. For example, a thermoplastic resin having good transparency, thermal stability, and stretchability can be used. Examples of the thermoplastic resin include an acrylic resin, a polyolefin resin, a polyester resin, a polyvinyl alcohol resin, or a mixture thereof.

A-5. Other

In one embodiment, unwinding the resin substrate from the resin substrate roll (the unwinding step), heating the resin substrate (the heating step), and forming a PVA-based resin layer (the PVA-based resin layer forming step) are continuously performed. According to the said embodiment, the said heat processing effect can be acquired favorably. A specific example of this embodiment may be the one shown in FIG. 4 as an example: the steps of unwinding, heating, and forming a PVA-based resin layer are sequentially performed on a series of production lines for conveying a long resin substrate. The laminated body manufacturing apparatus 100 shown in FIG. 4 includes a take-up roll 40, a heating device 50, The coating device 60, the drying device 70, and the coiling roller 80; the unwinding roller 40 is used to roll out the resin substrate 11 from the resin substrate roll 30, and the heating device 50 is used to heat the resin substrate 11 The coating device 60 is used to apply a coating solution containing the PVA-based resin to the surface of the resin substrate 11, the drying device 70 is used to dry the applied coating solution, and the coiled roller 80 is used To roll bundle laminated body 10. In addition, the laminated body manufacturing apparatus 100 further includes a plurality of conveyance rollers 90.

B. Stretching the laminate

The stretched laminated body of the present invention is obtained by stretching the above-mentioned laminated body. In one embodiment, the stretched laminated body is produced by stretching the laminated body by an aerial stretching method at a stretching ratio of 1.5 times to 3.0 times. The details of the laminated body stretching method are described later. In the stretched laminate, the film thickness of the PVA-based resin layer within the dimensions of 200 mm (MD) x 200 mm (TD) is preferably 0.25 μm or less, and more preferably 0.20 μm or less. In the stretched laminate, the retardation axis of the PVA-based resin layer in the dimension of 200 mm (MD) × 200 mm (TD) should be 0.50 ° or less, more preferably 0.30 ° or less, and even more preferably 0.25 ° or less.

C. Polarizing film

The polarizing film of the present invention is produced by performing a process for forming the PVA-based resin layer of the laminated body into a polarizing film.

Examples of the treatment for forming a polarizing film include dyeing treatment, stretching treatment, insolubilization treatment, crosslinking treatment, washing treatment, and drying treatment. These treatments can be appropriately selected depending on the purpose. Moreover, the processing order, processing timing, number of processing times, and the like can be appropriately set. Each process is explained below.

(Dyeing treatment)

The dyeing process is typically performed by dyeing a PVA-based resin layer with a dichroic substance. This is preferably performed by adsorbing a dichroic substance on the PVA-based resin layer. Examples of the adsorption method include a method of immersing a PVA-based resin layer (layered body) in a dyeing solution containing a dichroic substance, a method of coating the dyeing solution on a PVA-based resin layer, and spraying the dyeing solution on a PVA-based Method of resin layer, etc. The method of immersing the laminated body in the dyeing solution is preferable. This is because dichroic substances can be adsorbed well.

Examples of the dichroic material include iodine and organic dyes. These can be used alone or in combination of two or more kinds. The dichroic substance is preferably iodine. When using iodine as a dichroic substance, the above-mentioned dyeing solution is preferably an iodine aqueous solution. The blending amount of iodine is preferably 0.05 to 5.0 parts by weight with respect to 100 parts by weight of water. In order to improve the solubility of iodine in water, it is suitable to mix iodide with iodine solution. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, titanium iodide, and the like. Among them, potassium iodide is preferred. The blending amount of the iodide is preferably 0.3 to 15 parts by weight relative to 100 parts by weight of water.

The temperature of the dyeing liquid when dyeing is preferably 20 ° C to 40 ° C. When the PVA-based resin layer is immersed in the dyeing solution, the immersion time should be 10 seconds to 300 seconds. Under these conditions, the dichroic substance can be sufficiently adsorbed by the PVA-based resin layer. In addition, the dyeing conditions (concentration, liquid temperature, and immersion time) can be set such that the polarization degree or monomer light transmittance of the finally obtained polarizing film is within a predetermined range. In one embodiment, the soaking time is set so that the polarization degree of the polarizing film to be produced can be 99.98% or more. In another embodiment, the soaking time is set such that The monomer light transmittance of the obtained polarizing film was about 40%.

(Stretching treatment)

Any appropriate method can be adopted as the method of stretching the laminated body. Specifically, fixed-end stretching (for example, a tenter stretching method) or free-end stretching (for example, a method of passing a laminated body through rollers with different peripheral speeds for uniaxial stretching) can be used. ). Moreover, simultaneous biaxial stretching (for example, a method using a simultaneous biaxial stretching machine) or sequential biaxial stretching may be adopted. Stretching of the laminate can be performed in one stage or in multiple stages. When carried out in multiple stages, the stretching ratio (maximum stretching ratio) of the laminated body described later is the product of the stretching ratios at each stage.

Stretching can be performed by immersing the laminate in a stretching bath. Under water stretching, aerial stretching can also be used. It is preferable to perform at least one underwater stretching treatment, and it is better to combine underwater stretching treatment and aerial stretching treatment. If it is stretched in water, it can be stretched at a temperature lower than the glass transition temperature of the resin substrate or PVA-based resin layer (typically about 80 ° C), thereby suppressing the crystallization of the PVA-based resin layer. It is stretched at a high magnification. As a result, a polarizing film having excellent optical characteristics (for example, polarization degree) can be manufactured.

The stretching direction of the laminated body can be selected from any appropriate direction. Yu Yi In the embodiment, it is stretched in the longitudinal direction of the long laminated body. Specifically, the laminated body is transported in the longitudinal direction, and the stretching direction is the transport direction (MD). In another embodiment, it is stretched in the width direction of the long laminated body. Specifically, the laminated body is transported in the longitudinal direction, and the stretching direction is the direction (TD) orthogonal to the transport direction (MD).

The stretching temperature of the laminated body can be set to any appropriate value according to the forming material and stretching method of the resin substrate. When the aerial stretching method is adopted, the stretching temperature should be above the glass transition temperature (Tg) of the resin substrate, the glass transition temperature (Tg) of the resin substrate + 10 ° C or more is more preferable, and the Tg + 15 ° C or more is more preferable. The stretching temperature of the laminate is preferably 170 ° C or lower. Stretching at the above temperature can suppress rapid crystallization of the PVA-based resin and suppress problems caused by the crystallization (for example, hinder the orientation of the PVA-based resin layer caused by stretching).

When the stretching method is an underwater stretching method, the liquid temperature of the stretching bath is preferably 40 ° C to 85 ° C, and more preferably 50 ° C to 85 ° C. If the temperature is the above-mentioned temperature, the PVA-based resin layer can be stretched at a high magnification while suppressing dissolution. Specifically, as described above, the glass transition temperature (Tg) of the resin substrate is preferably 60 ° C. or higher in relation to the formation of the PVA-based resin layer. At this time, if the stretching temperature is lower than 40 ° C, the resin substrate may not be stretched satisfactorily even if plasticizing of the resin base material is taken into consideration. In addition, the higher the temperature of the stretching bath, the higher the solubility of the PVA-based resin layer, and it may not be possible to obtain excellent optical characteristics.

When using the underwater stretching method, it is preferable to immerse the laminate in a boric acid aqueous solution for stretching (boric acid stretching in water). By using a boric acid aqueous solution as a stretching bath, the PVA-based resin layer can be given rigidity to withstand tension during stretching and water-insoluble water resistance. Specifically, boric acid can generate a tetrahydroxyborate anion in an aqueous solution, and can be crosslinked by hydrogen bonding with a PVA-based resin. As a result, it is possible to impart rigidity and water resistance to the PVA-based resin layer, to allow good stretching, and to obtain a polarizing film having excellent optical characteristics.

The above-mentioned aqueous boric acid solution is preferably prepared by dissolving boric acid and / or borate in water as a solvent. The boric acid concentration is preferably 1 to 10 parts by weight with respect to 100 parts by weight of water. When the boric acid concentration is 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizing film with better characteristics can be produced. In addition to boric acid or a borate, an aqueous solution prepared by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, etc. in a solvent may be used.

It is suitable to mix iodide in the stretching bath (aqueous boric acid solution). By mixing the iodide, the dissolution of the iodine that has been adsorbed in the PVA-based resin layer can be suppressed. Specific examples of the iodide are as described above. The concentration of the iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, with respect to 100 parts by weight of water.

The immersion time of the laminated body in the stretching bath is preferably 15 seconds to 5 minutes.

Relative to the original length of the laminate, the stretch ratio (maximum stretch ratio) of the laminate is typically 4.0 times or more, and preferably 5.0 times or more. Such a high stretching ratio can be achieved by, for example, using a water stretching method (stretching in boric acid). In addition, the "maximum stretching ratio" in this specification refers to the stretching ratio immediately before the laminated body is broken, and also refers to a value which is 0.2 lower than the value after confirming the stretching ratio of the laminated body that has broken.

The stretching treatment in water is preferably performed after the dyeing treatment.

(Insolubilization treatment)

The insolubilization treatment is typically performed by immersing a PVA-based resin layer in an aqueous boric acid solution. In particular, when the underwater stretching method is used, water resistance can be imparted to the PVA-based resin layer by performing an insolubilization treatment. The concentration of the boric acid aqueous solution The degree is preferably 1 to 4 parts by weight relative to 100 parts by weight of water. The liquid temperature of the insolubilization bath (aqueous boric acid solution) is preferably 20 ° C to 50 ° C. The insolubilization treatment is preferably performed after the laminated body is prepared and before the dyeing treatment and the water stretching treatment.

(Cross-linking treatment)

The crosslinking treatment is typically performed by immersing a PVA-based resin layer in an aqueous boric acid solution. By carrying out the crosslinking treatment, water resistance can be imparted to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight relative to 100 parts by weight of water. In addition, when the crosslinking treatment is performed after the above-mentioned dyeing treatment, it is preferable to further mix iodide. By mixing the iodide, the dissolution of the iodine that has been adsorbed in the PVA-based resin layer can be suppressed. The blending amount of the iodide is preferably 1 to 5 parts by weight relative to 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (aqueous boric acid solution) is preferably 20 ° C to 50 ° C. The crosslinking treatment is preferably performed before the underwater stretching treatment. In a preferred embodiment, a dyeing treatment, a crosslinking treatment, and an underwater stretching treatment are sequentially performed.

(Washing treatment)

The washing treatment is typically performed by immersing a PVA-based resin layer in an aqueous potassium iodide solution.

(Drying)

The drying temperature of the drying treatment is preferably 30 ° C to 100 ° C.

The obtained polarizing film is essentially a PVA-based resin film having a dichroic substance adsorbed and oriented. The thickness of the polarizing film is preferably 15 μm or less, more preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less. The polarizing film can suppress cracks and the like in an environmental test (for example, an environmental test at 80 ° C). The thickness of the polarizing film is preferably 0.5 μm or more, and more preferably 1.0 μm or more. The above-mentioned polarizing film has excellent transportability at the time of manufacture and the like.

The polarizing film should preferably be at any wavelength from 380nm to 780nm With absorption dichroism. When the monomer light transmittance is above 42%, the polarization degree of the polarizing film should be above 99.9%.

D. Polarizer

The polarizing plate of the present invention includes the above-mentioned polarizing film. The polarizing plate preferably has the above-mentioned polarizing film and a protective film disposed on at least one side of the polarizing film. This protective film may use the said resin base material directly, and may use the film different from the said resin base material. Examples of the material for forming the protective film include (meth) acrylic resins; cellulose resins such as cellulose diacetate and cellulose triacetate; cycloolefin resins; olefin resins such as polypropylene; polyethylene terephthalate Ester resins such as diester resins; polyamide resins; polycarbonate resins; and copolymer resins thereof. The thickness of the protective film is preferably 10 μm to 100 μm.

As described above, in one embodiment, the resin substrate is not peeled from the polarizing film, but it is directly used as a protective film. In another embodiment, the resin substrate is peeled from the polarizing film, and another film is laminated. The protective film may be laminated and laminated on the polarizing film through transmission and adhesion, or may be laminated in a state in which the protection film is adhered (not transmitted through the adhesion layer). The adhesive layer is typically formed with an adhesive or an adhesive. According to the present invention, a polarizing film having excellent thickness uniformity can be obtained, and therefore, a protective film can be laminated well on the polarizing film.

Examples

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited to these examples.

[Example 1-1] (Production of laminated body)

The resin substrate is made of amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) with a water absorption of 0.75% and a glass transition temperature (Tg) of 75 ° C, and the temperature is 115 ° C in advance. TD is stretched to 2.0 times and has a long shape and a thickness of 100 μm. The resin substrate is rolled into a roll with a tension of 100 N / m as a roll, and it is rolled at 25 ° C, Store at 60% RH for 30 days.

After that, the resin substrate was taken out from the resin substrate roll, and the resin substrate was conveyed and heat-treated at 70 ° C. for 60 seconds.

Next, a corona treatment is performed on one surface of the resin substrate. It will contain polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mole%) and acetamidine modified PVA (polymerization degree 1200, acetamidine modified 4.6%, saponification degree) at a ratio of 9: 1. Above 99.0 mol%, an aqueous solution manufactured by Nippon Synthetic Chemical Industry Co., Ltd. under the trade name "Gohsefimer Z200") is applied to the corona-treated surface by a die coating method at 25 ° C, and then dried at 60 ° C for 200 seconds to form a thickness of 10 µm. PVA-based resin layer to obtain a laminated body.

(Production of polarizing film)

The obtained laminated body was placed in an oven at 115 ° C., and the free end was uniaxially stretched to 2.0 times in the length direction between rollers with different peripheral speeds (air stretching).

Next, the layered product was immersed in an insolubilization bath (aqueous boric acid solution prepared by mixing 3 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 30 ° C (insolubilization treatment).

Next, immerse it in a dyeing bath (aqueous iodine solution prepared by mixing iodine and potassium iodide at a ratio of 1: 7 by weight in water) at a liquid temperature of 30 ° C, and adjust the iodine The concentration and immersion time were such that the monomer transmittance (Ts) of the polarizing film obtained was 40% or less (dyeing treatment).

Next, it was immersed in a crosslinking bath (aqueous boric acid solution prepared by mixing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 30 ° C (crosslinking treatment).

Thereafter, the laminate was immersed in a boric acid aqueous solution (aqueous solution prepared by mixing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 70 ° C, and passed between rollers having different peripheral speeds. Uniaxial stretching in the longitudinal direction was performed to 2.7 times (stretching in water).

Thereafter, the laminate was immersed in a washing bath (aqueous solution prepared by mixing 4 parts by weight of potassium iodide with 100 parts by weight of water with 100 parts by weight of water) at a liquid temperature of 30 ° C, and then dried at 60 ° C for 60 seconds (washing Cleaning and drying steps).

In this manner, a polarizing film having a thickness of 5 μm was formed on the resin substrate.

[Example 1-2]

When the laminated body was produced, the polarizing film was formed on the resin substrate in the same manner as in Example 1-1 except that the temperature of the heat treatment was set to 75 ° C.

[Example 1-3]

When the laminated body was produced, the polarizing film was formed on the resin substrate in the same manner as in Example 1-1 except that the temperature of the heat treatment was set to 80 ° C.

[Example 1-4]

When the laminated body was produced, the polarizing film was formed on the resin substrate in the same manner as in Example 1-1 except that the temperature of the heat treatment was set to 90 ° C.

[Example 1-5]

When producing a laminated body, in addition to setting the heat treatment temperature to 100 ° C, The remainder was the same as in Example 1-1, and a polarizing film was formed on a resin substrate.

[Example 2-1] (Production of laminated body)

A laminated body was prepared in the same manner as in Example 1-1.

(Formation of polarizing film)

The obtained laminated body was stretched to 4.0 times in the width direction by uniaxial stretching with a free end using a tenter stretcher under heating at 115 ° C (stretching treatment).

Next, the layered product was immersed in an insolubilization bath (aqueous boric acid solution prepared by mixing 3 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 30 ° C (insolubilization treatment).

Next, immerse it in a dyeing bath (aqueous iodine solution prepared by mixing iodine and potassium iodide at a ratio of 1: 7 by weight in water) at a liquid temperature of 30 ° C., and adjust the iodine concentration and the immersion time to make the obtained The unit light transmittance (Ts) of the polarizing film is 40% or less (dyeing treatment).

Next, it was immersed in a crosslinking bath (aqueous boric acid solution prepared by mixing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 30 ° C (crosslinking treatment).

Thereafter, the laminate was immersed in a washing bath (aqueous solution prepared by mixing 4 parts by weight of potassium iodide with 100 parts by weight of water with 100 parts by weight of water) at a liquid temperature of 30 ° C, and then dried at 60 ° C for 60 seconds (washing Cleaning and drying steps).

Thus, a polarizing film having a thickness of 2.5 μm was formed on the resin substrate.

[Example 2-2]

When the laminated body was produced, the polarizing film was formed on the resin substrate in the same manner as in Example 2-1 except that the temperature of the heat treatment was set to 75 ° C.

[Example 2-3]

When the multilayer body was produced, the polarizing film was formed on the resin substrate in the same manner as in Example 2-1 except that the temperature of the heat treatment was set to 100 ° C.

[Comparative Example 1-1]

When a laminated body was produced, the same procedure as in Example 1-1 was performed except that no heat treatment was performed. A polarizing film was formed on the resin substrate.

[Comparative Example 1-2]

When the laminated body was produced, the polarizing film was formed on the resin substrate in the same manner as in Example 1-1 except that the temperature of the heat treatment was set to 50 ° C.

[Comparative Example 1-3]

When the laminated body was produced, the polarizing film was formed on the resin substrate in the same manner as in Example 1-1 except that the temperature of the heat treatment was set to 55 ° C.

[Comparative Example 2-1]

When the laminated body was produced, the polarizing film was formed on a resin substrate in the same manner as in Example 2-1 except that the temperature of the heat treatment was set to 55 ° C.

(Evaluation)

The following evaluations were performed for each Example and Comparative Example.

1. Inconsistent film thickness

Using "MCPD3000" manufactured by Otsuka Electronics, the film thickness of the PVA-based resin layer after (I) coating with an aqueous polyvinyl alcohol solution and drying (before stretching) and (II) after aerial stretching was measured. The part containing the defective part (the part that originally had violent tendons) was cut out to a size of 200mm (MD) x 200mm (TD) as a measurement sample, and the MD and TD were measured with a film thickness of 1mm in the plane to evaluate the defect. The difference between the maximum film thickness and the minimum film thickness of the part.

2. Inconsistent slow axis and inconsistent absorption axis

Using "Axoscan" manufactured by Axometrics, Inc., measuring (I) the retardation axis direction of the PVA-based resin layer after applying a polyvinyl alcohol aqueous solution and drying (before stretching), and (II) the PVA-based resin layer after aerial stretching The retardation axis direction and (III) the absorption axis direction of the polarizing film. The part including the defective part was cut out to a size of 200 mm (MD) x 200 mm (TD) as a measurement sample, and the maximum axial direction difference of the defective part in the plane was measured. Regarding (I) and (II), after the PVA-based resin layer was bonded to the glass plate through the adhesive layer, the resin substrate was peeled and the hysteresis axis of the PVA-based resin layer was measured.

3. Appearance

The appearances of (I) the PVA-based resin layer after the polyvinyl alcohol aqueous solution was applied and dried (before stretching), (II) the PVA-based resin layer after aerial stretching, and (III) the polarizing film were visually observed.

Regarding (I) and (II), as shown in FIG. 5 (a), in a state where a commercially available polarizing plate is stacked on top of the laminated body (sample), light is irradiated from below and visually observed from above. At this time, it is arrange | positioned so that the absorption axis of two polarizing plates may become orthogonal, and the extending direction of a laminated body and the absorption axis of a lower polarizing plate may be orthogonal.

Regarding (III), as shown in FIG. 5 (b), in a state where a commercially available polarizing plate is laminated under the laminated body (sample), light is irradiated from below and visually viewed from above. At this time, the absorption axis of the polarizing film arranged as a laminated body and the absorption axis of the lower polarizing plate are orthogonal to each other.

The evaluation criteria shown in Table 1 are as follows.

○: The inconsistencies in the defective parts cannot be seen

×: It can be seen that the inconsistencies are inconsistent

4. Polarization

Using a spectrophotometer (manufactured by Murakami Color Research Laboratory, trade name "Dot-41"), the single transmittance (Ts), parallel transmittance (Tp), and orthogonal transmittance of the polarizing film (Tc), and the degree of polarization (P) was obtained by the following formula. These transmittances are Y values measured in accordance with JIS Z 8701's 2-degree field of view (C light source) and corrected for visual sensitivity.

Polarization (P) = ((Tp-Tc) / (Tp + Tc)) ^1/2 × 100

In the examples, the film thickness of the PVA-based resin layer was inconsistent, the retardation axis was not consistent, and the absorption axis was not uniform at all time points. Moreover, its appearance is also good. In addition, the occurrence of wrinkles was confirmed visually in Examples 1-5 and 2-3. The wrinkles may be caused by thermal wrinkles that occur in the resin substrate due to heat treatment.

Industrial availability

The polarizing film of the present invention is suitable for, for example, an image display device. Specifically, it is suitable for use in LCD TVs, LCD monitors, mobile phones, LCD panels for cameras, camcorders, portable game consoles, car navigation, copiers, printers, fax machines, clocks, microwave ovens, etc., and reflection prevention panels for organic EL devices.

Claims (16)

A method for manufacturing a laminated body, which sequentially includes the following steps: a heating step of heating a resin substrate to a glass transition temperature (Tg) of the resin substrate of -15 ° C or higher; and a polyvinyl alcohol-based resin layer forming step, in A polyvinyl alcohol-based resin layer is formed on the resin substrate; the manufacturing method is to carry out the heating step while conveying the resin substrate by a conveying roller provided in a heating furnace, and the holding of the conveying roller in the heating furnace The angle is 90 ° or more. The manufacturing method according to claim 1, wherein the resin substrate is rolled out from a resin substrate roll formed by winding a long resin substrate into a roll shape, and the heating step is performed. The manufacturing method according to claim 2 is performed after the aforementioned heating step after storage in the aforementioned bundle state. The manufacturing method as claimed in claim 2, wherein the unwinding step, the heating step, and the polyvinyl alcohol-based resin layer forming step are continuously performed. The manufacturing method according to claim 1, wherein the heating step is performed at a glass transition temperature (Tg) of the resin substrate + 15 ° C or lower. The manufacturing method according to claim 1, wherein the distance between the centers of the conveying rollers in the heating furnace is 2 m or less. The manufacturing method according to claim 1, wherein the shrinkage ratio of the resin substrate by the aforementioned heating is 3% or less. The method according to claim 1, wherein the resin substrate is formed of a polyethylene terephthalate resin. The manufacturing method as claimed in claim 1, wherein the aforementioned resin substrate is stretched in advance. The method according to claim 1, wherein the polyvinyl alcohol-based resin layer is formed by applying a coating solution containing a polyvinyl alcohol-based resin on the resin substrate by a die coating method and drying the coating liquid. A method for manufacturing a polarizing film, which uses a multilayer body produced by the manufacturing method according to claim 1. The method for manufacturing a polarizing film according to claim 11, comprising a step of stretching the laminated body. A method for manufacturing a polarizing plate includes a step of laminating a protective film on a polarizing film, and the polarizing film is manufactured according to the method for manufacturing a polarizing film as claimed in claim 11. An apparatus for manufacturing a laminated body, comprising: a unwinding mechanism for unwinding the resin base material from a resin base material roll formed by winding a long resin base material into a roll shape; a heating furnace provided with The heating roller is used for conveying the long resin substrate, and the heating furnace heats the resin substrate to a glass transition temperature (Tg) of the resin substrate of -15 ° C or higher; and the coating mechanism is A coating liquid containing a polyvinyl alcohol-based resin is coated on the resin substrate; and the holding angle of the transfer roller in the heating furnace is 90 ° or more. The manufacturing apparatus according to claim 14, wherein the resin substrate is transferred by a transfer roller installed in the heating furnace and heated at the same time. The manufacturing apparatus according to claim 14, wherein the center-to-center distance between the conveying rollers in the heating furnace is 2 m or less.